The present invention relates to a method of magnetic recording/reproducing. More particularly, the present invention relates to a method of magnetic recording/reproducing which attains a high S/N ratio in a system in which signals recorded in a coated-type magnetic recording medium (i.e., a magnetic recording particulate medium) for high-density recording are reproduced with an MR head.
In the field of magnetic disks, 2-MB MF-2HD floppy disks employing a cobalt-modified iron oxide have come to be mounted as a standard external storage medium in personal computers. However, as a result of the recent rapid increase of the quantity of data to be dealt with, the capacity of the floppy disks has become insufficient. There has hence been a desire for a capacity increase in floppy disks.
In the field of magnetic tapes also, investigations are recently being made enthusiastically on magnetic tapes as external storages for recording computer data (the so-called backup tapes), with the spread of minicomputers, personal computers, and office computers such as work stations. For practically using magnetic tapes in such applications, there is an especially strong desire for an improvement in recording capacity for attaining an increased recording capacity and a reduced recording-medium size, besides the desire for a size reduction and an increase in information-processing ability in computers.
Magnetic recording media heretofore in wide use comprise a nonmagnetic support and, formed thereover by coating, a magnetic layer comprising a binder and dispersed therein iron oxide, cobalt-modified iron oxide, CrO2, ferromagnetic metal particles, or hexagonal-ferrite particles. Of these magnetic materials, fine particles of hexagonal ferrites are known to have excellent high-density recording characteristics. However, in recording/reproducing with an inductive head which has hitherto been mainly used in the systems employing flexible media, the fine particles of a hexagonal ferrite have a low saturation magnetization and a sufficient output has not been obtained therewith.
In the removable recording employing such flexible media, however, the magnetoresistive heads (MR heads) in use with hard disks have come to be used. Since MR heads have high sensitivity, a sufficient reproduction output is obtained even with use of fine particles of a hexagonal ferrite. It is known that due to the noise reduction characteristic of hexagonal ferrites, a high C/N ratio is obtained. For example, Japanese Patent Application (Laid-Open) No. 302243/1998 discloses a technique which employs fine particles of barium ferrite (BaFe) and uses an MR head for reproduction.
The design of the MR heads heretofore in use is based on a thin magnetic film or acicular ferromagnetic alloy particles, and there is a desire for an MR head design optimized for barium ferrite particles.
An object of the present invention is to provide a method of magnetic recording/reproducing which is for a coated-type magnetic recording medium (i.e., a magnetic recording particulate medium) with excellent productivity for use in a system of recording/reproducing with an MR head and which attains satisfactory electromagnetic characteristics and a greatly improved S/N ratio especially in a high-density recording region.
The present invention provides a method of magnetic recording/reproducing which comprises reproducing with a magnetoresistive head (MR head) signals recorded in a magnetic recording medium comprising a support having thereon a magnetic layer comprising mainly ferromagnetic particles and a binder, wherein the MR head has an element thickness of 50 nm or smaller and the ferromagnetic particles are hexagonal-ferrite magnetic particles having an average tabular diameter of from 10 to 40 nm and an average tabular thickness smaller than the element thickness of the MR head used for reproduction.
In a preferred embodiment of the present invention, the method of magnetic recording/reproducing is applied to a magnetic recording medium in which the magnetic layer has a machine direction coercive force Hc of from 158 to 350 kA/m and an average thickness of from 30 to 300 nm.
According to the method of magnetic recording/reproducing of the present invention, signals can be recorded at a high density due to the use of fine hexagonal-ferrite magnetic particles having an average tabular diameter as small as from 10 to 40 nm, and the signals recorded m can be reproduced with an MR head while diminishing the noise in the reproduced signals because the magnetic particles have an average tabular thickness smaller than the element thickness (50 nm or smaller) of the MR head. Furthermore, by regulating the magnetic layer so as to have a coercive force Hc of from 158 to 350 kA/m and an average thickness of from 30 to 300 nm, the method of magnetic recording/reproducing can be made to attain an increased linear recording density, freedom from MR head saturation, and excellent suitability for overwriting.
In case where the hexagonal-ferrite magnetic particles in the recording medium for use in the present invention have an average tabular diameter of smaller than 10 nm, it is difficult to obtain stable magnetic recording by the cause of thermal fluctuations. On the other hand, average tabular diameters of the magnetic particles exceeding 40 nm result in a decrease in S/N, impaired suitability for overwriting, and reduced resolution.
In case where the MR head to be used in the present invention has an element thickness exceeding 50 nm, resolution is impaired.
The thickness of the magnetic layer is desirably small from the standpoint of improving resolution in overwriting and short-wavelength recording. A specific technique for attaining a reduction in magnetic-layer thickness is to form a substantially nonmagnetic lower layer between a magnetic layer and a support, as has been known. This technique is more preferred in that it attains reduced surface roughness and improved productivity.
As stated above, the noise in reproduced signals can be diminished by regulating the hexagonal-ferrite magnetic particles so as to have an average tabular thickness smaller than the element thickness of the MR head. The reason for this is that due to such a small average tabular thickness, a larger number of magnetic particles are present in the unit length for magnetic flux revolution which are detectable by the element.
The term xe2x80x9celement thickness of the MR headxe2x80x9d means the thickness as measured along the head travel direction.
Examples of MR heads usable in the present invention include anisotropic MR heads and shield type MR heads.
Although the MR head to be used in the method of magnetic recording/reproducing of the present invention is not particularly limited, a thin-film magnetic head of the electromagnetic induction type such as, e.g., an MIG head is advantageously used.
The magnetic recording medium to be used in the present invention will be explained below in detail.
Magnetic Layer
The magnetic recording medium may have a magnetic layer either on one side only or on each side of the support. When a magnetic layer is to be formed on a lower layer, a coating solution for forming the magnetic layer (also called xe2x80x9cupper layerxe2x80x9d or xe2x80x9cupper magnetic layerxe2x80x9d) may be applied either by the wet-on-wet (W/W) method in which it is applied while a coating solution for lower-layer formation which has been applied is still in a wet state or by the wet-on-dry (W/D) method in which the coating solution for magnetic-layer formation is applied after the coating solution for lower-layer formation applied has been dried. From the standpoint of production efficiency, simultaneous or successive wet-on-wet coating is preferred. In the case of disks, however, the wet-on-dry coating method also is sufficient. The use of simultaneous or successive wet-on-wet (W/W) coating in forming a multilayer constitution is advantageous in that surface-treating steps including a calendering step can be effectively conducted because the upper and lower layers can be formed simultaneously. Thus, the resulting upper magnetic layer can have improved surface roughness even when exceedingly thin.
In order for the magnetic recording medium to have a magnetic layer as thin as from 30 to 300 nm, it preferably has a multilayer constitution including a nonmagnetic layer. The coercive force Hc of the magnetic layer is preferably from 158 to 350 kA/m (2,000 to 4,430 Oe), more preferably from 170 to 280 kA/m. Furthermore, the magnetic layer has preferably been regulated so as to have such a magnetization distribution that the amount of components which undergo a magnetic flux revolution upon application of a magnetic field of 80 kA/M (1,000 Oe) or lower is less than 1%, preferably 0.7% or smaller, more preferably 0.5% or smaller.
The thickness of the magnetic layer is preferably from 30 to 300 nm, more preferably from 50 to 250 nm, most preferably from 50 to 200 nm. Thicknesses thereof smaller than 30 nm result in an insufficient reproduction output. In case where the thickness thereof is larger than 300 nm, a phase difference arises between the magnetizable component present in inner parts of the layer and the magnetizable component present in surface parts of the layer, resulting in enhanced waveform asymmetry. In addition, the degree of erasion by overwriting decreases.
Ferromagnetic Particles
The ferromagnetic particles used in the magnetic layer are particles of a hexagonal ferrite. Examples thereof include substitution products of barium ferrite, strontium ferrite, lead ferrite, or calcium ferrite and cobalt substitution products. Specific examples thereof include barium ferrite and strontium ferrite each of the magnetoplumbite type, magnetoplumbite-type ferrites whose surface has been coated with spinel, and magnetoplumbite-type barium ferrite and strontium ferrite each partly containing a spinel phase. Such ferrites may contain atoms of elements other than the given elements. Examples of such optional elements include Al, Si, S, Sc, Ti, V, Cr, Cu, Y, Mo, Rh, Pd, Ag, Sn, Sb, Te, Ba, Ta, W, Re, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, P, Co, Mn, Zn, Ni, Sr, B, Ge, and Nb. In general, ferrites to which elements such as Coxe2x80x94Zn, Coxe2x80x94Ti, Coxe2x80x94Tixe2x80x94Zr, Coxe2x80x94Tixe2x80x94Zn, Nixe2x80x94Tixe2x80x94Zn, Nbxe2x80x94Znxe2x80x94Co, Sbxe2x80x94Znxe2x80x94Co, or Nbxe2x80x94Zn have been added can be used. Some ferrites contain peculiar impurities depending on raw materials or production processes.
The term xe2x80x9caverage tabular diameterxe2x80x9d used for the hexagonal-ferrite magnetic particles means the average of the tabular diameters of the hexagonal tabulars. The average tabular diameter thereof is from 10 to 40 nm, preferably from 10 to 35 nm, more preferably from 15 to 35 nm. Especially in the case where an MR head is used for reproduction in order to attain an increased track density, the tabular diameter is preferably 35 nm or smaller because of the necessity of noise reduction. However, in case where the average particle diameter thereof is smaller than 10 nm, thermal fluctuations occur and stable magnetization cannot hence be expected. On the other hand, average tabular diameters thereof exceeding 40 nm result in increased noises and are hence unsuitable for high-density magnetic recording.
The average tabular thickness of the magnetic particles is smaller than the element thickness of the MR head to be used for reproduction, and is preferably 80% or less, more preferably 60% or less, of the thickness of the MR head. The smaller the average tabular thickness, the more the magnetic particles are preferred. Virtually, however, the average tabular thickness is 3 nm or larger.
The average tabular ratio (arithmetic mean of tabular diameter/tabular thickness) of the magnetic particles is desirably from 1 to 15, preferably from 1 to 7. Although small values of the average tabular ratio are preferred from the stand point of attaining a higher packing property in the magnetic layer, sufficient orientation cannot be obtained therewith. On the other hand, values of the average tabular ratio larger than 15 result in increased noises due to particle stacking. When the magnetic particles have a size within that range, the particles have a specific surface area as measured by the BET method (SBET) of from 10 to 100 m2/g. The specific surface area roughly agrees with the arithmetic mean calculated from the particle tabular diameter and tabular thickness. The narrower the particle tabular diameter/tabular thickness distribution, the more the magnetic particles are usually preferred. A numerical comparison can be made by measuring arbitrarily selected five hundred particles on a TEM photograph of each particulate material. Although many particulate magnetic materials do not have a normal distribution, the magnetic particles to be used in the present invention are ones whose coefficient of variance represented by standard deviation based on the calculated average tabular diameter ("sgr"/average tabular diameter or average tabular thickness) is generally from 0.1 to 2.0, preferably from 0.1 to 1.0, more preferably from 0.1 to 0.5. For obtaining magnetic particles having a narrow particle size distribution, a technique is being used in which a reaction system for particle formation is kept as even as possible and the particles yielded are subjected to a treatment for distribution improvement. Examples of this treatment include a method in which the particles are treated with an acid solution to selectively dissolve ultrafine particles therein. The hexagonal-ferrite fine particles have an average particle volume of generally from 1,000 to 10,000 nm3, preferably from 1,500 to 8,000 nm3, more preferably from 2,000 to 8,000 nm3.
Magnetic materials having a coercive force Hc of about from 40 to 400 kA/m can usually be produced. Although higher values of Hc are advantageous for high-density recording, Hc is limited by the capacity of the recording head to be used. In the present invention, the Hc of the magnetic material is about from 120 to 360 kA/m, preferably from 158 to 350 kA/m. When a head having a saturation magnetization exceeding 1.4 T is to be used, it is preferred to employ a magnetic material having an Hc of 175 kA/m or higher. Hc can be regulated by regulating particle size (tabular diameter/tabular thickness), the kind and amount of an element incorporated, the substitution site for the element, reaction conditions for particle formation, etc. The saturation magnetization "sgr"s of the magnetic material is generally from 40 to 80 A.m2/kg. The finer the particles, the more the "sgr"s tends to become low. Well well-known techniques for improving "sgr"s include to combine a magnetoplumbite ferrite with a spinel ferrite and to select the kind and amount of an element to be incorporated. It is also possible to use a W-type hexagonal ferrite. Furthermore, a technique is being used in which before a magnetic material is dispersed, the surface of the magnetic particles is treated with a substance suitable for the dispersion medium and polymer to be used. As the surface-treating agent, is used an inorganic compound or an organic compound. Representative examples of such compounds include the oxides or hydroxides of silicon, aluminum, and phosphorus, various silane coupling agents, and various titanium coupling agents.
The amount of the surface-treating agent to be used may be from 0.1 to 10% based on the magnetic material. The pH of the magnetic material also is important for dispersion. The optimal value of pH is generally in the range of about from 4 to 12 depending on the dispersion medium and polymer to be used. However, a pH of about from 6 to 11 is selected from the standpoints of the chemical stability of the medium and storage stability. The water content of the magnetic material also influences dispersibility. A water content of from 0.01 to 2.0% is generally selected although the optimal value thereof depends on the dispersion medium and polymer to be used. Examples of processes for producing a hexagonal ferrite include: a glass crystallization method which comprises mixing starting materials such as barium oxide, iron oxide, an oxide of a metal with which iron is to be substituted, and boron oxide as a glass-forming substance so as to result in a desired ferrite composition, melting the mixture, rapidly cooling the melt to form an amorphous material, and subsequently subjecting the amorphous material to a heat treatment and then to washing and pulverizing to thereby obtain a crystalline powder of barium ferrite; a hydrothermal reaction method which comprises neutralizing a solution of metal salts having a barium ferrite composition with an alkali, removing the by-product, subsequently heating the mixture in a liquid phase at 100xc2x0 C. or higher, and then subjecting the mixture to washing, drying, and pulverization to obtain a crystalline powder of barium ferrite; and a coprecipitation method which comprises neutralizing a solution of metal salts having a barium ferrite composition with an alkali, removing the by-product, subsequently drying the mixture, treating the reaction product at 1,100xc2x0 C. or lower, and then pulverizing it to obtain a crystalline powder of barium ferrite. The hexagonal ferrite to be used in the present invention may be one produced by any process.
Nonmagnetic Layer
The nonmagnetic layer which may be formed as a lower layer between the support and the magnetic layer will be explained below in detail. The lower layer is not particularly limited in constitution as long as it is substantially nonmagnetic. However, it usually comprises at least a resin. Preferred examples thereof include a layer comprising a resin and particles, e.g., inorganic particles or organic particles, dispersed in the resin. Although the inorganic particles are usually preferably nonmagnetic particles, magnetic particles may be used as long as the lower layer is substantially nonmagnetic.
The nonmagnetic particles can be selected, for example, from inorganic compounds such as metal oxides, metal carbonates, metal sulfates, metal nitrides, metal carbides, and metal sulfides. Examples of such inorganic compounds include xcex1-alumina having an xcex1-alumina having an xcex1-conversion rate of 90% or higher, xcex2-alumina, xcex3-alumina, xcex8-alumina, silicon carbide, chromium oxide, cerium oxide, xcex1-iron oxide, hematite, goethite, corundum, silicon nitride, titanium carbide, titanium oxide, silicon dioxide, tin oxide, magnesium oxide, tungsten oxide, zirconium oxide, boron nitride, zinc oxide, calcium carbonate, calcium sulfate, barium sulfate, and molybdenum disulfide. These inorganic compounds may be used alone or in combination of two or more thereof. Especially preferred are titanium dioxide, zinc oxide, the iron oxides, and barium sulfate from the standpoints of the narrowness of particle size distribution and the availability of many techniques for function impartation. More preferred of these are titanium dioxide and a-iron oxide. The particle size of such nonmagnetic particles is preferably from 0.005 to 2 xcexcm. However, particulate nonmagnetic materials differing in particle size may be used in combination according to need. Alternatively, a single particulate nonmagnetic material having a widened particle diameter distribution may be used so as to produce the same effect. Especially preferred nonmagnetic particles have a particle size of from 0.01 to 0.2 xcexcm. Especially when the nonmagnetic particles are a granular metal oxide, the average particle diameter thereof is preferably 0.08 xcexcm or smaller. When the nonmagnetic particles are an acicular metal oxide, the long-axis length thereof is preferably 0.3 xcexcm or shorter, more preferably 0.2 xcexcm or shorter. The tap density thereof is generally from 0.05 to 2 g/mL, preferably from 0.2 to 1.5 g/mL. The water content of the nonmagnetic particles is generally from 0.1 to 5% by weight, preferably from 0.2 to 3% by weight, more preferably from 0.3 to 1.5% by weight. The pH of the nonmagnetic particles is generally from 2 to 11, and is preferably in the range of from 5.5 to 10.
The specific surface area of the nonmagnetic particles is generally from 1 to 100 m2/g, preferably from 5 to 80 m2/g, more preferably from 10 to 70 m2/g. The crystallite size of the nonmagnetic particles is preferably from 0.004 to 1 xcexcm, more preferably from 0.04 to 0.1xcexcm. The oil absorption amount thereof as measured with DBP (dibutyl phthalate) is generally from 5 to 100 mL/100 g, preferably from 10 to 80 mL/10 g, more preferably from 20 to 60 mL/100 g. The specific gravity thereof is generally from 1 to 12, preferably from 3 to 6. The particle shape thereof may be any of acicular, spherical, polyhedral, and platy shapes. The Mohs"" hardness thereof is preferably from 4 to 10. The nonmagnetic particles have an SA (stearic acid) adsorption amount of generally from 1 to 20 xcexcmol/m2, preferably from 2 to 15 xcexcmol/m2, more preferably from 3 to 8 xcexcmol/m2. The pH thereof is preferably in the range of from 3 to 6. The nonmagnetic particles are preferably subjected to a surface treatment to thereby cause Al2O3, SiO2, TiO2, ZrO2, SnO2, Sb2O3, ZnO, or Y2O3 to be present on the surface of the particles. Especially preferred are Al2O3, SiO2, TiO2, and ZrO2 from the standpoint of enhancing dispersibility. More preferred of these are Al2O3, SiO2, and ZrO2. These may be used in combination of two or more thereof or may be used alone.
The surface treatment may be conducted by suitable methods according to purposes. For example, a surface treatment in layer formed by coprecipitation may be used. Alternatively, use may be made of a method in which alumina is deposited first and this surface layer is then treated with silica or a method in which the alumina treatment and silica treatment are conducted in the reversed order. Although a porous surface treatment layer may be formed according to purposes, it is generally preferred to form a surface treatment layer which is homogeneous and dense.
Specific examples of the nonmagnetic particles for use in the lower layer include Nanotite manufactured by Showa Denko K. K.; HIT-100 and ZA-G1 manufactured by Sumitomo Chemical Co., Ltd.; xcex1-hematite DPN-250, DPN-250BX, DPN-245, DPN-270BX, DPN-500BX, DBN-SA1, and DBN-SA3 manufactured by Toda Kogyo Corp.; titanium oxide TTO-51B, TTO-55A, TTO-55B, TTO-55C, TTO-55S, TTO-55D, and SN-100 and xcex1-hematite E270, E271, E300, and E303 manufactured by Ishihara Sangyo Kaisha, Ltd.; titanium oxide STT-4D, STT-30D, STT-30, and STT-65C and xcex1-hematite xcex1-40 manufactured by Titan Kogyo K. K.; MT-100S, MT-100T, MT-150W, MT-500B, MT-600B, MT-100F, and MT-500HD manufactured by Tayca Co., Ltd.; FINEX-25, BF-1, BF-10, BF-20, and ST-M manufactured by Sakai xcex1-Chemical Industry Co., Ltd.; DEFIC-Y and DEFIC-R manufactured by Dowa Mining Co., Ltd.; AS2BM and TiO2 P25 manufactured by Nippon Aerosil Co., Ltd.; 100A and 500A manufactured by Ube Industries, Ltd.; and nonmagnetic materials obtained by burning these. Especially preferred nonmagnetic particles are titanium dioxide particles and xcex1-iron oxide particles.
A carbon black may be incorporated into the lower layer, whereby the well-known effects of lowering the surface electrical resistance Rs and reducing the light transmittance can be produced and, simultaneously therewith, a desired value of micro-Vickers hardness can be obtained. It is also possible to incorporate a carbon black into the lower layer to thereby enable the layer to have the effect of storing a lubricant therein. Examples of the kinds of carbon blacks usable in the present invention include furnace black for rubbers, thermal black for rubbers, coloring black, and acetylene black. The carbon black to be incorporated into the lower layer should be one which has been optimized with respect to the following properties according to the desired effect. Use of a combination of two or more carbon blacks may produce an enhanced effect.
The carbon black to be incorporated into the lower layer has a specific surface area of generally from 100 to 500 m2/g, preferably from 150 to 400 m2/g, and a DBP absorption amount of generally from 20 to 400 mL/100g, preferably from 30 to 400 mL/100g. The particle diameter of the carbon black is generally from 5 to 80 nm, preferably from 10 to 50 nm, more preferably from 10 to 40 nm. The carbon black preferably has a pH of from 2 to 10, a water content of from 0.1 to 10%, and a tap density of from 0.1 to 1 g/mL. Specific examples of carbon blacks usable in the present invention include BLACKPEARLS 2000, 1300, 1000, 900, 800, 880, 700, and VULCAN XC-72 manufactured by Cabot Corp.; #3050B, #3150B, #3250B, #3750B, #3950B, #950, #650B, #970B, #850B, MA-600, MA-230, #4000, and #4010 manufactured by Mitsubishi Chemical Industries Ltd.; CONDUCTEX SC, RAVEN 8800, 8000, 7000, 5750, 5250, 3500, 2100, 2000, 1800, 1500, 1255, and 1250manufactured by Columbian Carbon Co.; and Ketjen Black EC manufactured by Akzo N. V. Such carbon blacks may be surface-treated with a dispersant or the like or grafted with a resin before use. A carbon black whose surface has been partly graphitized may also be used.
Before being added to a coating solution, the carbon black may be dispersed in a binder. Those carbon blacks can be used in an amount of 50% by weight or less based on the inorganic particles and in an amount of 40% by weight or less based on the total amount of the nonmagnetic layer. Those carbon blacks can be used alone or in combination of two or more thereof. With respect to carbon blacks usable in the present invention, reference may be made to, for example, Kxc3xa2bon Burakku Binran (edited by Carbon Black Association, Japan).
Organic particles may be added to the lower layer according to purposes. Examples thereof include acrylic/styrene resin particles, benzoguanamine resin particles, melamine resin particles, and phthalocyanine pigments. Also usable are polyolefin resin particles, polyester resin particles, polyamide resin particles, polyimide resin particles, and poly(fluoroethylene) resins. For producing such organic particles, processes such as those described in Japanese Patent Application (Laid-Open) Nos. 18564/1987 and 255827/1985 may be used.
Binder resins, lubricants, dispersants, additives, solvents, methods for dispersion, and others usable for forming the lower layer may be the same as those for the magnetic layer which will be described later. In particular, with respect to the amounts and kinds of binder resins and the amounts and kinds of additives and dispersants, well-known techniques for forming magnetic layers are applicable.
Binder
As the binder for the present invention is used any of well-known thermoplastic resins, thermosetting resins, and reactive resins and mixtures of these. The thermoplastic resins are ones having a glass transition temperature of from xe2x88x92100 to 150xc2x0 C., a number-average molecular weight of from 1,000 to 200,000, preferably from 10,000 to 100,000, and a degree of polymerization of about from 50 to 1,000.
Examples of such thermoplastic resins include polymers or copolymers comprising units of one or more of vinyl chloride, vinyl acetate, vinyl alcohol, maleic acid, acrylic acid, acrylic acid esters, vinylidene chloride, acrylonitrile, methacrylic acid, methacrylic acid esters, styrene, butadiene, ethylene, vinyl butyral, vinyl acetal, and vinyl ethers as constituent units, and further include polyurethane resins and various rubbery resins. Examples of the thermosetting resins or reactive resins include phenolic resins, epoxy resins, curable polyurethane resins, urea resins, melamine resins, alkyd resins, reactive acrylic resins, formaldehyde resins, silicone resins, epoxy-polyamide resins, mixtures of a polyester resin and an isocyanate prepolymer, mixtures of a polyester polyol and a polyisocyanate, and mixtures of a polyurethane and a polyisocyanate. These resins are described in detail in Purasuchikku Handobukku, published by Asakura Shoten. Well-known electron beam-curable resins may be used for forming each layer. Examples of these resins and processes for producing these are described in detail in Japanese Patent Application (Laid-Open) No. 256219/1987. The resins enumerated above may be used alone or in combination of two or more thereof. However, preferred examples thereof include combinations of at least one member selected from vinyl chloride resins, vinyl chloride/vinyl acetate copolymers, vinyl chloride/vinyl acetate/vinyl alcohol copolymers, and vinyl chloride/vinyl acetate/maleic anhydride copolymers with a polyurethane resin, and further include combinations of the at least one member, a polyurethane resin, and a polyisocyanate.
The polyurethane resin may have a well-known structure such as a polyester polyurethane, polyether polyurethane, polyether polyester polyurethane, polycarbonate polyurethane, polyester polycarbonate polyurethane, or polycaprolactone polyurethane. For obtaining further improved dispersibility and durability, it is preferred to use, according to need, one or more of the above-enumerated binders which have, incorporated therein through copolymerization or addition reaction, polar groups of at least one kind selected from xe2x80x94COOM, xe2x80x94SO3M, xe2x80x94OSO3M, xe2x80x94Pxe2x95x90O(OM)2, xe2x80x94Oxe2x80x94Pxe2x95x90O(OM)2 (wherein M is a hydrogen atom or an alkali metal), OH, NR2, N+R3 (R is a hydrocarbon group), an epoxy group, SH, CN, and the like. The amount of such polar groups is from 10xe2x88x921 to 10xe2x88x928 mol/g, preferably from 10xe2x88x922 to 10xe2x88x926 mol/g.
Specific examples of those binders that can be used in the present invention include VAGH, VYHH, VMCH, VAGF, VAGD, VROH, VYES, VYNC, VMCC, XYHL, XYSG, PKHH, PKHJ, PKHC, and PKFE manufactured by Union Carbide Corp.; MPR-TA, MPR-TA5, MPR-TAL, MPR-TSN, MPR-TMF, MPR-TS, MPR-TM, and MPR-TAO manufactured by Nisshin Chemical Co., Ltd.; 1000W, DX80, DX81, DX82, DX83, and 100FD manufactured by Denki Kagaku Kogyo K.K.; MR-104, MR-105, MR110, MR100, MR555, and 400X-11OA manufactured by Nippon Zeon Co., Ltd.; Nippollan N2301, N2302, and N2304 manufactured by Nippon Polyurethane Industry Co. Ltd.; Pandex T-5105, T-R3080, T-5201, Burnock D-400, D-210-80, Crisvon 6109, and 7209 manufactured by Dainippon Ink and Chemicals, Inc.; Vylon UR8200, UR8300, UR8700, RV530, and RV280 manufactured by Toyobo Co., Ltd.; Daiferamine 4020, 5020, 5100, 5300, 9020, 9022, and 7020 manufactured by Dainichiseika Kogyo K.K.; MX5004 manufactured by Mitsubishi Chemical Industries Ltd.; Sunprene SP-150 manufactured by Sanyo Chemical Industries, Ltd.; and Salan F310 and F210 manufactured by Asahi Chemical Industry Co., Ltd.
The amount of the binder to be used for forming the nonmagnetic layer or magnetic layer is in the range of generally from 5 to 50% by weight (i.e., by mass), preferably from 10 to 30% by weight, based on the nonmagnetic particles or the ferromagnetic particles. In the case of employing a vinyl chloride resin, it is preferred to use the resin in an amount of from 5 to 30% by weight in combination with from 2 to 20% by weight polyurethane resin and from 2 to 20% by weight polyisocyanate. However, a polyurethane alone or a combination of a polyurethane and an isocyanate alone may be used, for example, when there is a possibility that a slight amount of chlorine might be released to cause head corrosion. In the case of using a polyurethane in the present invention, this resin is desirably one having a glass transition temperature of from xe2x88x9250 to 150xc2x0 C., preferably from 0 to 100xc2x0 C., more preferably from 30 to 90xc2x0 C., an elongation at break of from 100 to 2,000%, a stress at break of from 0.05 to 10 kg/mm2 (0.49 to 98 MPa), and a yield point of from 0.05 to 10 kg/mm2 (0.49 to 98 MPa).
The magnetic recording medium can have two or more coating layers. Consequently, it is, of course, possible to form the individual layers so that these layers differ from each other in binder amount, the proportion of a vinyl chloride resin, polyurethane resin, polyisocyanate, or another resin in the binder, the molecular weight and polar group content of each resin contained in the magnetic layer, the aforementioned physical properties of a resin, etc., according to need. Rather than being thus regulated, these factors should be optimized for each layer. For attaining this, well-known techniques concerning multilayered magnetic layers are applicable. For example, in the case of forming layers having different binder amounts, an increase in binder amount in the magnetic layer is effective in diminishing the scratches of the magnetic layer surface, while an increase in binder amount in the nonmagnetic layer is effective in imparting flexibility thereto and thereby improving head touching.
Examples of the polyisocyanate include isocyanates such as tolylene diisocyanate, 4,4xe2x80x2-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, naphthylene-1,5-diisocyanate, o-toluidine diisocyanate, isophorone diisocyanate, and triphenylmethane triisocyanate, products of the reactions of these isocyanates with polyhydric alcohols, and polyisocyanates formed through condensation of isocyanates. These isocyanates are commercially available under the trade names of: Coronate L, Coronate HL, Coronate 2030, Coronate 2031, Millionate MR, and Millionate MTL manufactured by Nippon Polyurethane Industry Co., Ltd.; Takenate D-102, Takenate D-110N, Takenate D-200, and Takenate D-202 manufactured by Takeda Chemical Industries, Ltd.; and Desmodule L, Desmodule IL, Desmodule N, and Desmodule HL manufactured by Sumitomo Bayer Co., Ltd. For each layer, these polyisocyanates may be used alone, or used in combination of two or more thereof, taking advantage of a difference in curing reactivity.
Carbon Black, Abrasive Material
The carbon black for use in the magnetic layer may be furnace black for rubbers, thermal black for rubbers, coloring black, acetylene black, or the like. The carbon black preferably has a specific surface area of from 5 to 500 m2/g, a DBP absorption amount of from 10 to 400 mL/100 g, an average particle diameter of from 5 to 300 nm, preferably from 10 to 250 nm, more preferably from 20 to 200 nm, a pH of from 2 to 10, a water content of from 0.1 to 10%, and a tap density of from 0.1 to 1 g/ml. Specific examples of carbon blacks usable in the present invention include BLACKPEARLS 2000, 1300, 1000, 900, 905, 800, 700, and VULCAN XC-72 manufactured by Cabot Corp.; #80, #60, #55, #50, and #35 manufactured by Asahi Carbon Co., Ltd.; #2400B, #2300, #900, #1000, #30, #40, and #10B manufactured by Mitsubishi Chemical Industries Ltd.; CONDUCTEX SC, RAVEN 150, 50, 40, and 15, and RAVEN-MT-P manufactured by Columbian Carbon Co.; and Ketjen Black EC manufactured by Japan EC Co. These carbon blacks may be surface-treated with a dispersant or another agent or grafted with a resin before use. A carbon black whose surface has been partly graphitized may also be used.
Before being added to a magnetic coating solution, the carbon black may be dispersed in a binder. Those carbon blacks can be used alone or in combination. In the case of using a carbon black, its amount is preferably from 0.1 to 30% based on the magnetic material. The carbon black incorporated in the magnetic layer functions to prevent static change in the layer, to reduce the coefficient of friction of the layer, to impart a light shielding property for the layer, and to improve the film strength. Such effects are produced to different degrees depending on the kind of carbon black used. Consequently, it is, of course, possible in the present invention to properly use carbon blacks according to purposes so as to give an upper magnetic layer and a lower nonmagnetic layer which differ in the kind, amount, and combination of carbon blacks, on the basis of the aforementioned properties including particle size, oil absorption amount, electrical conductivity, and pH. Rather than being thus regulated, these factors should be optimized for each layer. With respect to carbon blacks usable in the magnetic layer, reference may be made to, for example, Kxc3xa2bon Burakku Binran (edited by Carbon Black Association).
Abrasive materials usable in the present invention are well-known abrasive materials mostly having a Mohs"" hardness of 6 or higher. Examples thereof include xcex1-alumina having an xcex1-conversion rate of 90% or higher, xcex2-alumina, silicon carbide, chromium oxide, cerium oxide, xcex1-iron oxide, corundum, artificial diamond, silicon nitride, silicon carbide, titanium carbide, titanium oxide, silicon dioxide, and boron nitride. These may be used alone or in combination. A composite made up of two or more of these abrasive materials (e.g., one obtained by surface-treating one abrasive material with another) may also be used. Although in some cases these abrasive materials contain compounds or elements other than the main component, the same effect is obtained with such abrasive materials as long as the content of the main component is 90% or higher. These abrasive materials have a particle size of preferably from 0.01 to 2 xcexcm, more preferably from 0.05 to 1.0 xcexcm, most preferably from 0.05 to 0.5xcexcm. An abrasive material having a narrower particle size distribution is preferred especially for enhancing electromagnetic characteristics. For improving durability, abrasive materials having different particle sizes may be used in combination according to need. Alternatively, a single abrasive material having a widened particle diameter distribution may be used so as to produce the same effect. The abrasive material to be used preferably has a tap density of from 0.3 to 2 g/ml, a water content of from 0.1 to 5%, a pH of from 2 to 11, and a specific surface area of from 1 to 30 m2/g. Although abrasive materials that can be used in the present invention may have any particle shape selected from the acicular, spherical, and dice forms, a particle shape having a sharp corner as part of the contour is preferred because abrasive materials of this shape have high abrasive properties. Specific examples of abrasive materials usable in the present invention include AKP-12, AKP-15, AKP-20, AKP-30, AKP-50, HIT 20, HIT-30, HIT-55, HIT 60, HIT 70, HIT 80, and HIT 100, manufactured by Sumitomo Chemical Co., Ltd.; ERC-DBM, HP-DBM, and HPS-DBM manufactured by Reynolds Co.; WA 10000 manufactured by Fujimi Kenmazai Kogyo K. K.; UB 20 manufactured by C. Uyemura and Co., Ltd.; G-5, Kromex U2, and Kromex U1 manufactured by Nippon Chemical Industrial Co., Ltd.; TF100 and TF140 manufactured by Toda Kogyo Corp.; xcex2-Random Ultra fine manufactured by Ibiden Co., Ltd.; and B-3manufactured by Showa Industry Co., Ltd. These abrasive materials may be added also to the nonmagnetic layer according to need. The incorporation of an abrasive material in the nonmagnetic layer has the effect of regulating the surface shape or regulating the projecting state of an abrasive material. The particle diameter and amount of the abrasive material to be added to each of the magnetic layer and the nonmagnetic layer should, of course, be optimized.
Additives
Additives having a lubricating, antistatic, dispersing, plasticizing, or another effect may be used in the magnetic layer and non magnetic layer. Examples of such additives include molybdenum disulfide, tungsten disulfide, graphite, boron nitride, fluorinated graphite, silicone oils, silicones having a polar group, fatty acid-modified silicones, fluorine-containing silicones, fluorine-containing alcohols, fluorine-containing esters, polyolefins, polyglycols, esters of alkylphosphoric acids and alkali metal salts of the esters, esters of alkylsulfuric acids and alkali metal salts of the esters, poly(phenyl ether)s, phenylphosphonic acid, xcex1-naphthylphosphoric acid, phenylphosphoric acid, diphenylphosphoric acid, p-ethylbenzenephosphonic acid, phenylphosphinic acid, aminoquinones, various silane coupling agents, titanium coupling agents, fluorine-containing alkylsulfuric acid esters and alkali metal salts of the esters, monobasic fatty acids having 10 to 24 carbon atoms (which may have an unsaturated bond or be branched) and metal salts (e.g., lithium, sodium, potassium, or copper salts) of these acids, mono-, di-, tri-, tetra-, penta-, and hexahydric alcohols having 12 to 22 carbon atoms (which may have an unsaturated bond or be branched), alkoxyalcohols having 12 to 22 carbon atoms, mono-, di-, or triesters of a monobasic fatty acid having 10 to 24 carbon atoms (which may have an unsaturated bond or be branched) with any one of mono-, di-, tri-, tetra-, penta-, and hexahydric alcohols having 2 to 12 carbon atoms (which may have an unsaturated bond or be branched), fatty acid esters of monoalkyl ethers of alkylene oxide polymers, fatty acid amides having 8 to 22 carbon atoms, and aliphatic amines having 8 to 22 carbon atoms.
Examples of the fatty acids include capric acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenicacid, oleicacid, elaidicacid, linoleicacid, linolenic acid, and isostearic acid. Examples of the esters include butyl stearate, octyl stearate, amyl stearate, isooctyl stearate, butyl myristate, octyl myristate, butoxyethyl stearate, butoxydiethyl stearate, 2-ethylhexyl stearate, 2-octyldodecyl palmitate, 2-hexyldodecyl palmitate, isohexadecyl stearate, oleyl oleate, dodecyl stearate, tridecyl stearate, erucic acid oleyl, neopentyl glycol didecanoate, and ethylene glycol dioleate. Examples of the alcohols include oleyl alcohol, stearyl alcohol, and lauryl alcohol. Surfactants are also usable. Examples thereof include nonionic surfactants such as those of the alkylene oxide type, glycerol type, glycidol type, and alkylphenol ethylene oxide adduct type; cationic surfactants such as cyclic amines, ester amides, quaternary ammonium salts, hydantoin derivatives, heterocyclic compounds, and phosphonium or sulfonium compounds; anionic surfactants containing an acid radical such as a carboxylic acid, sulfonic acid, phosphoric acid, sulfate, or phosphate radical; and amphoteric surfactants such as amino acids, aminosulfonic acids, esters of sulfuric or phosphoric acid with amino-alcohols, and alkylbetaines. These surfactants are described in detail in Kaimen Kasseizai Binran (published by Sangyo Tosho K. K.). These additives including lubricants and antistatic agents need not be 100% pure, and may contain impurities such as isomers, unreacted products, by-products, decomposition products, oxidation products, etc., besides the main components. The content of these impurities is desirably 30% or lower, preferably 10% or lower.
Those lubricants and surfactants usable in the present invention have different physical functions, and the kinds and amounts of such ingredients and a lubricant proportion for producing a synergistic effect should be optimized according to purposes. Lubricants or surfactants may be used, for example, in the following manners: fatty acids having different melting points are used for the nonmagnetic layer and the magnetic layer, respectively, to control the bleeding to the surface; esters differing in boiling point, melting point, or polarity are used to control the bleeding to the surface; surfactant amounts are regulated to improve the stability of coating; and a larger lubricant amount is used for an interlayer to obtain an improved lubricating effect. It is a matter of course that manners of using lubricants or surfactants are not limited to these examples. In general, the total amount of the lubricants to be used is selected from the range of from 0.1 to 50%, preferably from 2 to 25%, based on the magnetic material or the nonmagnetic particles.
Part or all of the additives to be used in the present invention may be added at any step in the course of the production of a magnetic coating solution or nonmagnetic coating solution. Examples of addition techniques include: to mix the additives with a magnetic material prior to a kneading step; to add the additives during the step of kneading a magnetic material together with a binder and a solvent; to add the additives at a dispersing step; to add the additives after dispersion; and to add the additives immediately before coating. Some purposes may be accomplished by forming a magnetic layer by coating and then applying part or all of one or more additives simultaneously or successively according to the purposes. It is also possible to apply a lubricant to the surface of the magnetic layer after calendering or after completion of slitting, according to purposes. Well-known organic solvents can be used in the present invention. For example, the solvents shown in Japanese Patent Application (Laid-Open) No. 68453/1994 can be used.
Layer Constitution
In the layer constitution of the magnetic recording medium, the support has a thickness of generally from 2 to 100 xcexcm, preferably from 2 to 80 xcexcm. For computer tapes, a support having a thickness in the range of generally from 3.0 to 6.5 xcexcm (preferably from 3.0 to 6.0 xcexcm, more preferably from 4.0 to 5.5 xcexcm) is used.
An undercoat layer may be formed between the support and the nonmagnetic layer or magnetic layer for the purpose of improving adhesion. This undercoat layer has a thickness of generally from 0.01 to 0.5 xcexcm, preferably from 0.02 to 0.5 xcexcm. The recording medium to be used in the present invention may be a disk-form medium produced by forming a nonmagnetic layer and a magnetic layer on each side of a support, or may be a tape-form or disk-form medium produced by forming these layers on only one side of a support. In the latter case, a back coat layer may be formed on the side opposite to the nonmagnetic layer and magnetic layer for the purpose of producing an antistatic effect, anticurling effect, etc. This back coat layer has a thickness of generally from 0.1 to 4 xcexcm, preferably from 0.3 to 2.0 xcexcm. The undercoat layer and back coat layer each may be a well-known layer.
The nonmagnetic layer has a thickness of generally from 0.2 to 5.0 xcexcm, preferably from 0.3 to 3.0 xcexcm, more preferably from 1.0 to 2.5 xcexcm. The nonmagnetic layer produces its effects as long as it is substantially nonmagnetic. For example, the nonmagnetic layer may contain a slight amount of a magnetic material either as an impurity or as an ingredient purposely incorporated. It is a matter of course that such constitution can be regarded as substantially the same as that of the recording medium in which the nonmagnetic layer contains no magnetic material. The term xe2x80x9csubstantially nonmagneticxe2x80x9d as used herein generally means that the residual magnetic flux density of the nonmagnetic layer is 0.01 T or lower or the coercive force thereof is 7.96 kA/m (100 Oe) or lower, and preferably means that the nonmagnetic layer has no residual magnetic flux density and no coercive force.
Back Coat Layer
Compared to video tapes and audio tapes, the magnetic tapes for computer data recording generally are strongly required to have a high degree of suitability for repetitions of running. For maintaining the high degree of running durability required, the back coat layer preferably contains a carbon black and inorganic particles.
As the carbon black is preferably used a combination of two kinds of carbon blacks differing in average particle diameter. In this case, a preferred combination comprises a finely particular carbon black having an average particle diameter of from 10 to 20 nm and a coarse carbon black having an average particle diameter of from 230 to 300 nm. Addition of such a finely particulate carbon black is generally effective in regulating the back coat layer so as to have a low surface electrical resistance and a low light transmittance. Since there are many magnetic recording apparatus in which the light transmittance of a tape is utilized as a signal for operation, the addition of a finely particulate carbon black is especially effective in such a case. Furthermore, finely particulate carbon blacks generally have the high ability to hold a liquid lubricant and hence contribute to a reduction in coefficient of friction when a lubricant is used therewith in combination.
On the other hand, the coarse carbon black having an average particle diameter of from 230 to 300 nm not only functions as a solid lubricant but also forms minute projections on the surface of the back coat layer to reduce the contact area and thereby contribute to a reduction in coefficient of friction. However, use of the coarse carbon black alone has a drawback that when the tape is used under severe running conditions, carbon black particles are apt to fall down from the back coat layer due to tape sliding, leading to an increased error frequency.
Specific examples of commercial products of the finely particulate carbon black include the following. The average particle diameters thereof are shown in parentheses. RAVEN 2000B (18 nm) and RAVEN 1500B (17nm) (manufactured by Columbian Carbon Co.); BP 800 (17 nm) (manufactured by Cabot Corp.); PRINTEX 90 (14 nm), PRINTEX 95 (15 nm), PRINTEX 85 (16 nm), and PRINTEX 75 (17 nm) (manufactured by Degussa AG); and #3950 (16 nm) (manufactured by Mitsubishi Chemical Industries Ltd.).
Specific examples of commercial products of the coarse carbon black include Thermal Black (270 nm) (manufactured by Cancarb Ltd.) and RAVEN MTP (275 nm) (manufactured by Columbian Carbon Co.).
When a finely particulate carbon black and coarse carbon black which have average particle diameters of from 10 to 20 nm and from 230 to 300 nm, respectively, are used in the back coat layer as two kinds of carbon blacks differing in average particle diameter, then the proportion (by weight) of the former to the latter carbon black is preferably in the range of from 98:2 to 75:25, more preferably from 95:5 to 85:15.
The amount of the carbon black (total carbon black amount when two or more carbon blacks are used) in the back coat layer is generally from 30 to 80 parts by weight, preferably from 45 to 65 parts by weight, per 100 parts by weight of the binder.
The inorganic particles to be used preferably comprise a combination of two particulate materials differing in hardness. For example, it is preferred to use soft inorganic particles having a Mohs"" hardness of from 3 to 4.5 and hard inorganic particles having a Mohs"" hardness of from 5 to 9. Addition of the soft inorganic particles having a Mohs"" hardness of from 3 to 4.5 is effective in stabilizing the coefficient of friction during repetitions of running. In addition, such soft inorganic particles, which have a hardness within that range, do not abrade sliding guide poles. These inorganic particles preferably have an average particle diameter in the range of from 30 to 50 nm.
Examples of the soft inorganic particles having a Mohs"" hardness of from 3 to 4.5 include calcium sulfate, calcium carbonate, calcium silicate, barium sulfate, magnesium carbonate, zinc carbonate, and zinc oxide. These may be used alone or in combination of two or more thereof.
The amount of the soft inorganic particles contained in the back coat layer is in the range of preferably from 10 to 140 parts by weight, more preferably from 35 to 100 parts by weight, per 100 parts by weight of the carbon black.
Addition of the hard inorganic particles having a Mohs"" hardness of from 5 to 9 enhances the strength of the back coat layer to improve running durability. When these inorganic particles are used in combination with a carbon black and the soft inorganic particles described above, the back coat layer has improved durability with reduced deterioration in repetitions of sliding. Furthermore, the addition of the hard inorganic particles imparts a moderate abrading ability to the layer to thereby diminish the adhesion of scratched powders to tape guide poles, etc. Especially when the hard inorganic particles are used in combination with the soft inorganic particles, the back coat layer has improved sliding properties on guide poles having a rough surface, whereby the coefficient of friction of the back coat layer can also be stabilized.
The hard inorganic particles preferably have an average particle size in the range of from 80 to 250 nm (more preferably from 100 to 210 nm).
Examples of the hard inorganic particles having a Mohs"" hardness of from 5 to 9 include xcex1-iron oxide, xcex1-alumina, and chromium oxide (Cr2O3). These particulate materials may be used alone or in combination of two or more thereof. Preferred of these are xcex1-iron oxide and xcex1-alumina. The amount of the hard inorganic particles contained in the back coat layer is generally from 3 to 30 parts by weight, preferably from 3 to 20 parts by weight, per 100 parts by weight of the carbon black.
When soft inorganic particles and hard inorganic particles are to be used in combination in the back coat layer, these two kinds of inorganic particles are preferably ones selected so that the difference in hardness between the soft inorganic particles and the hard inorganic particles is 2 or more (more preferably 2.5 or more, most preferably 3 or more).
The back coat layer preferably contains the two particulate inorganic materials differing in Mohs"" hardness and each having a specific average particle size and further contains the two carbon blacks differing in average particle size.
A lubricant can be incorporated into the back coat layer. One or more lubricants suitably selected from the lubricants enumerated above as lubricants usable in the nonmagnetic layer or magnetic layer described above may be used. The amount of the lubricant to be added to the back coat layer is generally from 1 to 5 parts by weight per 100 parts by weight of the binder.
Support
The support used in the present invention is not particularly limited. However, the support is preferably a substantially nonmagnetic flexible support.
As the flexible support for use in the present invention can be employed a well-known film. Examples thereof include films of polyesters such as poly(ethylene terephthalate) and poly (ethylene naphthalate), polyolefins, cellulose triacetate, polycarbonates, aromatic polyamides, aliphatic polyamides, polyimides, poly(amide-imide)s, polysulfones, and polybenzoxazole. Preferred of these are high-strength supports made of poly(ethylene naphthalate), a polyamide, or the like. A laminate support such as that described in Japanese Patent Application (Laid-Open) No. 224127/1991 may be used according to need so that the magnetic layer surface and the base surface differ in surface roughness. These supports may be subjected beforehand to corona discharge treatment, plasma treatment, easy adhesion treatment, heat treatment, dust-removing treatment, etc. An aluminum or glass base may be also used as the support.
Supports advantageously usable are ones which have a central-plane average surface roughness Ra as measured with TOPO-3D, manufactured by WYKO Corp., of generally 8.0 nm or lower, preferably 4.0 nm or lower, more preferably 2.0 nm or lower. Besides having such a low central-plane average surface roughness, these supports are required to be preferably free from projections as large as 0.5 xcexcm or more. The state of the surface roughness can be freely controlled by regulating the size and amount of a filler which is incorporated into the support according to need. Examples of the filler include oxides or carbonates of calcium, silicon, and titanium and fine organic powders such as acrylic powders. The support preferably has a maximum height Rmax of 1 xcexcm or smaller, a ten-point average roughness Rz of 0.5 xcexcm or lower, a central-plane peak height Rp of 0.5 xcexcm or smaller, a central-plane valley depth Rv of 0.5 xcexcm or smaller, a central-plane a real ratio Sr of from 10 to 90%, and an average wavelength xcexa of from 5 to 300 xcexcm. The surface projections on the support can be controlled with a filler so as to have any desired distribution, for the purpose of obtaining the desired electromagnetic characteristics and durability. The number of surface projections respectively having sizes of various ranges of from 0.01 xcexcm to 1 xcexcm can be regulated so as to be from 0 to 2,000 per 0.1 mm2. The support to be used in the present invention has an F-5 value of preferably from 5 to 50 kg/mm2 (49 to 490 MPa). The degree of thermal shrinkage of the support as measured under the conditions of 100xc2x0 C. and 30 minutes is preferably 3% or lower, more preferably 1.5% or lower, and the degree of thermal shrinkage thereof as measured under the conditions of 80xc2x0 C. and 30 minutes is preferably 1% or lower, more preferably 0.5% or lower. The strength at break of the support is preferably from 5 to 100 kg/mm2 (=about 49 to 980 MPa), and the modulus of elasticity thereof is preferably from 100 to 2,000 kg/mm2 (=about a 0.98 to 19.6 GPa). The thermal expansivity of the support is generally from 10xe2x88x924 to 10xe2x88x928/xc2x0 C., preferably from 10xe2x88x925 to 10xe2x88x926/xc2x0 C., and the hygroexpansivity thereof is generally 10xe2x88x924/RH % or lower, preferably 10xe2x88x925/RH % or lower. It is preferred that the support be almost homogeneous in each of these thermal, dimensional, and mechanical properties in such a degree that the difference in each property between any in-plane directions in the support is within 10%.
Process for Production
A process for producing a magnetic coating solution or nonmagnetic coating solution to be used for producing the magnetic recording medium comprises at least a kneading step and a dispersing step, and may further comprise a mixing step which may optionally be conducted before and after the two steps. Each step may include two or more stages. Each of the materials for use in the present invention, including a magnetic material, nonmagnetic particles, binder, carbon black, abrasive material, antistatic agent, lubricant, and solvent, may be added in any step either at the beginning of or during the step. Furthermore, each raw material maybe added portion-wise in two or more steps. For example, a polyurethane may be added portion-wise so that it is added in each of the kneading step, dispersing step, and mixing step for viscosity adjustment after the dispersion. Well-known manufacturing techniques can be used as part of the process. In the kneading step is preferably used a kneading machine having a high kneading power, such as an open kneader, continuous kneader, pressure kneader, or extruder. In the case of using a kneader, the magnetic material or nonmagnetic particles are kneaded together with all or part (preferably at least 30%) of the binder, the binder amount being in the range of from 15 to 500 parts per 100 parts of the magnetic material. Details of this kneading treatment are given in Japanese Patent Application (Laid-Open) Nos. 106338/1989 and 79274/1989. Although glass beads can be used for particle dispersion in preparing coating solutions respectively for forming a magnetic layer and a nonmagnetic layer, it is preferred to use zirconia beads, titania beads, or steel beads, which are dispersing media having a high specific gravity. Such a dispersing medium optimized in particle diameter is used in an optimal loading (i.e., filling rate). Well-known dispersing machines can be used.
In the case where a magnetic recording medium having a multilayer constitution according to the present invention is produced through coating, it is preferred to use any of the following methods.
The first method is to firstly form a lower layer through coating with a coating apparatus generally used for applying magnetic coating solutions, e.g., a gravure coating, roll coating, blade coating, or extrusion coating apparatus, and then form an upper layer, while the lower layer is still in a wet state, through coating with the support-pressing extrusion coater disclosed in Japanese Patent Publication No. 46186/1989 or a Japanese Patent Application (Laid-Open) No. 238179/1985 or 265672/1990.
The second method is to almost simultaneously form an upper layer and a lower layer through coating with a single coating head having therein two slits for passing coating solutions, such as those disclosed in Japanese Patent Application (Laid-Open) Nos. 88080/1988, 17971/1990, and 265672/1990.
The third method is to almost simultaneously form an upper layer and a lower layer through coating with the extrusion coater equipped with a back-up roll as disclosed in Japanese Patent Application (Laid-Open) No. 174965/1990.
For preventing the electromagnetic characteristics and other properties of the magnetic recording medium from being impaired by cohesion of magnetic particles, it is desirable to apply a shearing force to the coating solution in the coating head by a method such as those disclosed in Japanese Patent Application (Laid-Open) Nos. 95174/1987 and 236968/1989. The viscosity of each coating solution should be in the range specified in Japanese Patent Application (Laid-Open) No. 8471/1991.
For realizing a multilayer constitution, successive multiple coating may, of course, be used in which a coating solution is applied and dried to form a lower layer and a magnetic layer is then formed thereon. However, from the standpoint of diminishing coating defects to improve quality such as freedom from dropouts, it is preferred to use any of the techniques for simultaneous multiple coating described above.
In the case of producing a disk, it is preferred to use a well-known apparatus for random orientation in which magnetic particles are randomly oriented, for example, with cobalt magnets alternately arranged in oblique directions or by applying an alternating magnetic field with a solenoid, although sufficiently isotropic orientation is obtainable even without an orientation treatment with an orientation apparatus. In the case of fine ferromagnetic metal particles, the isotropic orientation generally preferably is in-plane two-dimensional random orientation but the particles can be three-dimensionally randomly oriented so as to include a vertically oriented component. Although hexagonal ferrites are generally apt to undergo three-dimensional random orientation with respect to in-plane and vertical directions, they can be two-dimensionally randomly oriented in in-plane directions. It is also possible to vertically orient the magnetic particles by a well-known technique, e.g., with heteropolar-facing magnets to impart magnetic properties which are isotropic in circumferential directions. Vertical orientation is preferred especially for high-density recording. Spin coating may be performed to conduct circumferential orientation.
In the case of a magnetic tape, a cobalt magnet or solenoid is used to orient the magnetic particles in the machine direction. It is preferred that the place in which the coating film is dried be made controllable by regulating the temperature and amount of the air fed for drying and the rate of coating. The rate of coating is preferably from 20 to 1,000 m/min and the temperature of the drying air is preferably 60xc2x0 C. or higher. Predrying may be performed to an appropriate degree before the coated support enters the magnet zone.
After the coating and drying, the magnetic recording medium is usually subjected to a calendering treatment. In the calendering treatment, the coated support is treated with plastic calendering rolls made of a heat-resistant plastic, e.g., an epoxy, polyimide, polyamide, or poly(imide-amide), or with metallic calendering rolls. Especially when the support has a magnetic layer on each side, the coated support is preferably calendered between metal rolls. The calendering temperature is preferably 50xc2x0 C. or higher, more preferably 100xc2x0 C. or higher. The linear pressure is preferably 200 kg/cm (196 kN/m) or higher, more preferably 300 kg/cm (294 kN/m) or higher.
Physical Properties
The saturation flux density of the magnetic layer in the magnetic recording medium according to the present invention is preferably from 0.1 to 0.3 T. The coercive force Hc of the magnetic layer is as stated hereinabove; narrower coercive force distributions are preferred, with the SFD being preferably 0.6 or lower. The squareness ratio of the magnetic layer in the case of two-dimensional random orientation is generally from 0.55 to 0.67, preferably from 0.58 to 0.64, and that in the case of three-dimensional random orientation is preferably from 0.45 to 0.55. In the case of vertical orientation, the vertical-direction squareness ratio of the magnetic layer is generally 0.6 or higher, preferably 0.7 or higher. In the case where the magnetic layer has undergone demagnetization field correction, the squareness ratio thereof is generally 0.7 or higher, preferably 0.8 or higher. In each of two-dimensional random orientation and three-dimensional random orientation, the orientation ratio is preferably 0.8 or higher. In the case of two-dimensional random orientation, each of the vertical-direction squareness ratio, Br, and Hc is preferably regulated to 0.1 to 0.5 times that in in-plane directions.
In the case of a magnetic tape, the squareness ratio of the magnetic layer is generally 0.7 or higher, preferably 0.8 or higher. The coefficient of friction of the magnetic recording medium with heads is generally 0.5 or lower, preferably 0.3 or lower, in the temperature range of from xe2x88x9210xc2x0 C. to 40xc2x0 C. and the humidity range of from 0 to 95%. The intrinsic surface resistivity of the magnetic recording medium on the magnetic layer side is preferably from 104 to 1012 xcexa9/sq, and the electrification potential thereof is preferably from xe2x88x92500 to +500 V. The modulus of elasticity at 0.5% elongation of the magnetic layer is preferably from 100 to 2,000 kg/mm2 (0.98 to 19.6 GPa) in any in-plane direction, and the strength at break thereof is preferably from 10 to 70 kg/mm2 (98 to 686 MPa). The modulus of elasticity of the magnetic recording medium is preferably from 100 to 1,500 kg/mm2 (0.98 to 14.7 GPa) in any in-plane direction, the residual elongation thereof is preferably 0.5% or lower, and the degree of thermal shrinkage thereof as measured at any temperature not higher than 100xc2x0 C. is preferably 1% or lower, more preferably 0.5% or lower, most preferably 0.1% or lower. The glass transition temperature (the temperature corresponding to a maximum of loss modulus in a dynamic viscoelasticity measurement made at 110 Hz) of the magnetic layer is preferably from 50 to 120xc2x0 C., while that of the lower nonmagnetic layer is preferably from 0 to 100xc2x0 C. The loss modulus is preferably in the range of from 1xc3x97109 to 8xc3x971010 pN/cm2, and the loss tangent is preferably 0.2 or smaller. Too large loss tangents tend to result in sticking troubles. It is preferred that the medium be almost homogeneous in each of these thermal and mechanical properties in such a degree that the difference in each property between any in-plane directions in the medium is within 10%. The residual solvent content in the magnetic layer is preferably 100 mg/m2 or lower, more preferably 10 mg/m2 or lower. The void content in each of the coating layers, i.e., the nonmagnetic layer and magnetic layer, is preferably 30% by volume or lower, more preferably 20% by volume or lower. Although a lower void content is desirable for attaining higher output, there are cases where a certain degree of void content is advantageous for some purposes. For example, in the case of disk media for which suitability for repetitions of running is important, higher void contents frequently bring about better running durability.
The central-plane average surface roughness Ra of the magnetic layer as measured with TOPO-3D, manufactured by WYKO Corp., over an area of about 250 xcexcmxc3x97250 xcexcm is generally 4.0 nm or lower, preferably 3.8 nm or lower, more preferably 3.5 nm or lower. The magnetic layer preferably further has a maximum height Rmax of 0.5 xcexcm or smaller, a ten-point average roughness Rz of 0.3 xcexcm or lower, a central-plane peak height Rp of 0.3 xcexcm or smaller, a central-plane valley depth Rv of 0.3 m or smaller, a central-plane a real ratio Sr of from 20 to 80%, and an average wavelength xcexa of from 5 to 300 xcexcm. The surface projections present on the magnetic layer are preferably regulated so as to meet those surface properties to thereby optimize the electromagnetic characteristics and coefficient of friction of the layer. The state of these surface projections can be easily controlled by controlling the surface state of the support with a filler and by regulating the particle diameter and amount of the filler to be added to the magnetic layer as stated above or regulating the surface shape of the rolls to be used for calendering, etc. The curling of the magnetic recording medium is preferably regulated so as to be within xc2x13 mm.
In the case where the magnetic recording medium has a nonmagnetic layer and a magnetic layer, it can be made to have a difference in any of those physical properties between the nonmagnetic layer and the magnetic layer according to purposes, as can be easily presumed. For example, the magnetic layer is made to have a heightened modulus of elasticity to improve running durability and, at the same time, the nonmagnetic layer is made to have a lower modulus of elasticity than the magnetic layer to improve the head touching of the magnetic recording medium.